Reduced temperature regernerating/calcining apparatus for hydrogen generation

ABSTRACT

A method and apparatus are disclosed for regenerating calcium oxide used in the production of hydrogen gas. The method includes steps of: (a) streaming a solid reactant into an inlet port of a contactor vessel; (b) streaming a purge oxidant into an oxidant port of the contactor vessel to reduce a partial pressure of a gas over the solid reactant; (c) venting the gas from a gas port of the contactor vessel; and (d) removing the solid reactant from a discharge port of the contactor vessel.

FIELD OF THE INVENTION

The present invention relates to the production of hydrogen gas. Morespecifically, the invention relates to a method and apparatus forregenerating the adsorbent reactant calcium oxide from calciumcarbonate, for example, to extract hydrogen from methane in a steammethane reformer.

BACKGROUND OF THE INVENTION

Hydrogen molecules and atoms are used in many commercial and industrialapplications. Generally, hydrogen may be used for upgrading petroleumfeed stock to more useful products. In addition, hydrogen is used inmany chemical reactions for reducing or synthesizing compounds. Forexample, hydrogen is a primary chemical reactant in the production ofcyclohexane, ammonia, and methanol. Moreover, hydrogen is recentlybecoming a fuel of choice because it reduces green house emissions.Specifically, hydrogen may be used in fuel cells and other similarapplications to produce a substantially clean source of electricity forpowering industrial machines and automobiles. Also, hydrogen may beincorporated into petroleum products to displace or remove sulfur,nitrogen, and unsaturated and aromatic chemicals, such as benzenes.

Several methods are known to remove or generate hydrogen fromhydrocarbon compounds. Although many sources of hydrocarbon compoundsmay be used to generate hydrogen, methane or natural gas is mostcommonly used. These gases travel easily through various mechanisms andalso serve as fuel in various reforming and generation processes.Hydrogen generation techniques generally include steam methane reformersand pressure swing absorbers. Other hydrogen production systems exploitthe byproducts from various industrial processes and the electricaldecomposition of water.

SUMMARY OF THE INVENTION

The present invention provides a method and apparatus that reduces thetemperature required for inducing a chemical reaction, for example, forcalcining a calcium compound in a reaction cooperator, advantageouslyprolonging the service life of the calcium compound and minimizing theamount of fuel required to maintain the temperature of the chemicalreaction.

In one embodiment of the present invention, an apparatus includes:

-   -   a contactor vessel;    -   an inlet port coupled to the contactor vessel for streaming a        solid reactant into the contactor vessel;    -   an oxidant port coupled to the contactor vessel for streaming a        purge oxidant into the contactor vessel to reduce a partial        pressure of a gas released from the solid reactant;    -   a gas port coupled to the contactor vessel for venting the gas        from the contactor vessel; and    -   a discharge port coupled to the contactor vessel for removing        the solid reactant from the contactor vessel.

In another embodiment of the present invention, a method includes stepsof: (a) streaming a solid reactant into an inlet port of a contactorvessel; (b) streaming a purge oxidant into an oxidant port of thecontactor vessel to reduce a partial pressure of a gas released from thesolid reactant; (c) venting the gas from a gas port of the contactorvessel; and (d) removing the solid reactant from a discharge port of thecontactor vessel.

In a further embodiment of the present invention, an apparatus includes:

-   -   means for containing a solid reactant during a separation        reaction;    -   means for streaming a solid reactant into the contactor vessel;    -   means for streaming a purge oxidant into the contactor vessel to        reduce a partial pressure of a gas released from the solid        reactant;    -   means for venting the gas from the contactor vessel; and    -   means for removing the solid reactant from the contactor vessel.

In another embodiment of the present invention, a method includesreducing the temperature required to sustain a calcining reaction byburning hydrogen in the contactor vessel to avoid generating combustionproducts that contain carbon dioxide.

DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

The present invention is illustrated by way of example and notlimitation in the accompanying figures, in which like referencesindicate similar elements throughout the several views of the drawings,and in which:

FIG. 1 illustrates a plot of carbon dioxide desorption partial pressurevs. temperature according to the prior art;

FIG. 2 illustrates a simplified schematic view of a counter-flowcalciner according to an embodiment of the present invention;

FIG. 3 illustrates a diagram of a hydrogen generator according to anembodiment of the present invention; and

FIG. 4 illustrates a flow chart of a method of calcining at a reducedtemperature according to an embodiment of the present invention.

Elements in the figures are illustrated for simplicity and clarity andhave not necessarily been drawn to scale. For example, the dimensions ofsome elements in the figures may be exaggerated relative to otherelements to point out distinctive features in the illustratedembodiments of the present invention.

DESCRIPTION OF THE ILLUSTRATED EMBODIMENTS

A pressure swing absorber (PSA) can generally produce a hydrogen productof about 99% pure hydrogen from a raw product gas that is subjected to awater separation to produce an inlet gas stream. The pressure swingabsorber separates the inlet gas stream into two separate gas streams: a99 percent pure hydrogen product stream and a byproduct gas streamcontaining the impurities that were removed from the inlet gas streamtogether with a substantial amount of hydrogen. The byproduct gas streamhas a relatively low pressure compared to the hydrogen product stream,and may be used as fuel for the calciner. A typical composition for thevarious gas streams is:

-   (1) Raw Product Gas Stream    -   0.68 dry gas fraction    -   0.922 hydrogen mole fraction    -   0.077 methane mole fraction    -   trace carbon monoxide and carbon dioxide mole fractions    -   ˜319 psia pressure at 310 degrees Fahrenheit temperature-   (2) Inlet Gas Stream    -   0.996 dry gas fraction    -   0.922 hydrogen mole fraction    -   0.077 methane mole fraction    -   trace carbon monoxide and carbon dioxide mole fractions    -   100 degrees Fahrenheit temperature-   (3) Hydrogen Product Gas Stream    -   99.99 percent hydrogen    -   <10 ppm carbon monoxide-   (4) Byproduct Gas Stream    -   0.614 hydrogen (30 percent of the heating value)    -   0.379 methane (70 percent of the heating value)

Generally, steam methane reformers (SMR) are used in large scaleindustrial processes to create the initial stream of hydrogen. Steammethane reformers generally produce less than 90% pure hydrogenmolecules in their product streams. The reforming of methane generallyproceeds according to the following reformation reaction:Reforming Reaction: CH₄+H₂O→CO+3H₂  (1)

The reforming reaction produces a first portion of hydrogen productstream from the steam reformation of methane.

A second portion of hydrogen product is produced by the reaction of thecarbon monoxide with steam:Shift Reaction: CO+H₂O reaction→CO₂+H₂  (2)

The gaseous carbon dioxide is vented from the solid calcium oxide, andthe regenerated calcium oxide is returned to the reaction cooperator.Typically, the calcination reaction is performed by heating the calciumcarbonate to a temperature of about 1100 degrees Centigrade. Reactions(1) and (2) are the two main reactions that produce the hydrogen productin a steam methane reformer.

The byproduct carbon dioxide (CO₂) may be removed from the hydrogenstream by a reaction cooperator. A typical reaction cooperator includescalcium oxide, which removes carbon dioxide from the shift reaction. Theremoval of carbon dioxide, also known as a separation reaction, proceedsas follows:Separation Reaction: CaO+CO₂→CaCO₃  (3)

The net reaction that occurs in a steam methane reformer, that is, thesum of the reactions (1) and (2), is given by:CH₄+2H₂O→CO₂+4H₂  (4)

Utilizing the carbon dioxide removal scheme with calcium oxide inaddition to methane and steam results in the following reaction:CH₄+2H₂O+CaO→4H₂+CaCO₃  (5)

Very little carbon dioxide and carbon monoxide are in the raw hydrogenproduct, which is mainly hydrogen, steam, and unreacted methane.

The product of the separation reaction is solid calcium carbonate, whilethe hydrogen product generated from the methane source is a gas. Thehydrogen gas is readily vented from the reaction cooperator, and thesolid calcium carbonate inside the reaction cooperator is replaced withregenerated calcium oxide.

The calcium oxide is typically regenerated from the calcium carbonate byheating the calcium carbonate to remove the carbon dioxide in a processcalled calcination. The calcination reaction proceeds as follows:Calcination Reaction: CaCO₃→CaO+CO₂  (6)

The gaseous carbon dioxide is vented from the solid calcium oxide, andthe regenerated calcium oxide is returned to the reaction cooperator.Typically, the calcination reaction (6) is performed by heating thecalcium carbonate to a temperature of about 1100 degrees Centigrade. Thecalcination reaction (6) is promoted by reducing the amount of carbon inthe fuel gas and the corresponding amount of carbon monoxide formed inthe calciner and by flowing the solid reactants through the calciner ina direction opposite from the flow of gases.

Using hydrogen as a fuel gas is beneficial in minimizing the carbondioxide partial pressure and temperature required for calcineroperation. Reducing the operating temperature of the calciner results inless sintering of the calcium oxide and a more reactive adsorbent in thecalciner. Because the calcium compound is used continuously in acyclical manner, sintering and corresponding reduction in reactivity isa cumulative process that requires periodically replacing the calciumcompound. If the calcium compound may be recycled 500 times, then it mayeasily be considered to be cost effective.

Operation of the hydrogen generator that supplies the inlet gas to thecalciner also results in very little carbon dioxide and carbon monoxideare generated in the hydrogen product. About 95 percent of the carbon inthe hydrogen combustion products is methane, therefore the byproduct gasfrom the pressure swing absorber that is used as fuel in the calcinerleaves minimal carbon dioxide per unit of heat content in the combustionproduct.

In a typical calciner operation of the prior art, the calcium carbonateformed from the separation reaction (3) is simply heated at atmosphericpressure to remove the carbon dioxide in the calcination reaction (6).Although this method is suitable for applications in which producingcalcium oxide is an end in itself, there are advantages that may berealized by the method of the present invention when the calcium oxideis to be used in the generation of hydrogen. For example, in a hydrogengenerator that produces hydrogen at a pressure of 25 to 30 atmospheres,it is desirable from an equipment configuration standpoint to performthe calcination at the same pressure so that the same vessel may be usedfor both hydrogen production and calcination.

FIG. 1 illustrates a plot 100 of carbon dioxide desorption partialpressure vs. temperature according to the prior art. Shown in FIG. 1 isa desorption curve 102.

In the area above the desorption curve 102, carbon dioxide is absorbedby calcium oxide to form calcium carbonate. In the area below thedesorption curve 102, carbon dioxide is desorbed, that is, released,from the calcium carbonate to form calcium oxide. As the partialpressure is increased, a higher temperature is required to maintain thecalcination reaction (4) in the area below the desorption curve 102.Normally, a higher temperature would be required to release the carbondioxide from the calcium carbonate under higher pressure as shown inFIG. 1. For example, at a partial pressure of about 200 psia, atemperature of about 1100 degrees Centigrade would be required toperform the calcination reaction (4).

A disadvantage of using a higher temperature to maintain the calcinationreaction (4) is that sintering occurs when the calcium oxide issubjected repeatedly to temperatures above about 700 degrees Centigrade.Sintering disadvantageously reduces the effective surface area of thecalcium oxide and decreases the carbon dioxide pore volume, reducing thecapability of the calcium oxide to readily adsorb carbon dioxide. As aresult, the performance of the regenerated calcium oxide is degraded insucceeding separation reaction cycles.

The disadvantages of the previous methods for regenerating calcium oxidefor hydrogen production may be mitigated or avoided by the method andapparatus of the present invention for hydrogen production thatincorporates calcination at a reduced temperature in the same contactorvessel as described below.

In one embodiment of the present invention, an apparatus includes:

-   -   a contactor vessel;    -   an inlet port coupled to the contactor vessel for streaming a        solid reactant into the contactor vessel;    -   an oxidant port coupled to the contactor vessel for streaming a        purge oxidant into the contactor vessel to reduce a partial        pressure of a gas released from the solid reactant;    -   a gas port coupled to the contactor vessel for venting the gas        from the contactor vessel; and    -   a discharge port coupled to the contactor vessel for removing        the solid reactant from the contactor vessel.

FIG. 2 illustrates a simplified schematic view of a counter-flowcalciner 200 according to an embodiment of the present invention. Shownin FIG. 2 are a contactor vessel 202, an inlet port 204, a gas port 206,a fuel port 208, a oxidant port 210, a rotary valve 212, a dischargeport 214, a heating zone 216, and a dilution zone 218.

The contactor vessel 202 may be, for example, a portion of a steammethane reformer. Alternatively, the contactor vessel 202 may be astandalone container suitable for containing the solid reactant underthe temperature and pressure conditions used in the calcining process.The contactor vessel 202 contains the solid reactant during thecalcination reaction (4) and is preferably oriented vertically toexploit the force of gravity for moving the solid reactant through thecontactor vessel 202, however other orientations of the contactor vesselmay be used to practice various embodiments of the present invention tosuit specific applications. The inlet port 204 is an opening in thecontactor vessel 202 that is used to receive a stream of solid reactant.In the example of FIG. 2, the solid reactant is calcium carbonate thatis streamed or flowed into the contactor vessel 202 from a hydrogenreactor at a pressure of from about 25 to 40 atmospheres. However, othersolid reactants besides calcium carbonate may be used to practicevarious embodiments of the present invention within the scope of theappended claims. The rotary valve 212 controls the rate of flow of thesolid reactant through the contactor vessel 202. The rate of flow of thesolid reactant through the rotary valve 212 is controlled according towell-known techniques, and the oxidized solid reactant is removed fromthe discharge port 214.

The fuel port 208 is an opening in the contactor vessel 202 that is usedto receive fuel, for example, hydrogen supplied from the stream ofunpurified hydrogen received by a steam methane reformer. The fuel isburned inside the contactor vessel 202 according to well-knowntechniques to heat the calcium carbonate to a temperature of about 950degrees Centigrade in the heating zone 216. Hydrogen is preferably usedas the fuel gas for the calciner, because its combustion products do notinclude carbon dioxide, thereby reducing the partial pressure of carbondioxide and the required operating temperature as illustrated in theplot of FIG. 1.

The oxidant port 210 is an opening in the contactor vessel 202 that isused to receive a purge oxidant, for example, steam. The purge oxidantreduces the partial pressure of the carbon dioxide released from theheated calcium carbonate. The purge oxidant may also be another suitablegas or vapor besides steam that preferably does not include the gasbeing released from the solid reactant, in this example, carbon dioxide.The purge oxidant agitates the solid reactant in the dilution zone 218and displaces the carbon dioxide gas released from the calcium carbonatetoward the gas port 206. At the gas port 206, the carbon dioxide and thepurge oxidant are vented and evacuated from the contactor vessel 202according to well-known techniques.

In this example, the gas port 206 is located so that the released gasflows in a direction opposite that of the flow of the solid reactant inthe contactor vessel 202, however, other locations of the gas port 206may be selected to practice various embodiments of the present inventionwithin the scope of the appended claims. The displacement of the carbondioxide gas away from the calcium carbonate by the purge oxidant resultsin a reduction of the partial pressure of carbon dioxide gas releasedfrom the calcium carbonate. For example, the partial pressure of carbondioxide gas released from the calcium carbonate may be reduced to apartial pressure of about 5 to 6 psia.

The reduction of the partial pressure of the carbon dioxide gas releasedfrom the solid reactant is an important feature of the presentinvention, because the reduced partial pressure allows the calcinationreaction (4) to proceed at a substantially lower temperature relative tothe pressure inside the contactor vessel 202. For example, a temperatureof about 1150 degrees Centigrade used in a conventional calciner may bedecreased to about 950 degrees Centigrade in a calciner of the presentinvention by the reduction of the partial pressure of the carbon dioxidegas released from the solid reactant. The lower required temperatureadvantageously results in lower fuel costs and significantly reducessintering the calcium oxide, especially in view of the fact that thedegree of sintering has been found to increase exponentially withtemperature. As a result, the regenerated calcium oxide may be used in agreater number of hydrogen production cycles, thereby reducing the costof replacing the calcium oxide.

In another aspect of the present invention, a method includes steps of:(a) streaming a solid reactant into an inlet port of a contactor vessel;(b) streaming a purge oxidant into an oxidant port of the contactorvessel to oxidize the solid reactant by reducing a partial pressure of agas around the solid reactant; (c) venting the gas from a gas port ofthe contactor vessel; and (d) removing the solid reactant from adischarge port of the contactor vessel.

FIG. 3 illustrates a diagram of a hydrogen generator 300 according to anembodiment of the present invention. Shown in FIG. 3 are a calcinersection 302, a methane/steam inlet 304, a primary bed 304, a gas port306, a fuel port 308, a rotary valve 310, a discharge port 312, ahydrogen outlet port 314, and an inlet port 316.

In FIG. 3, the solid reactant calcium carbonate is received from theinlet port 316 and heated by burning fuel from the fuel port 308 tooxidize the calcium carbonate and regenerate the calcium oxide. Theregenerated calcium oxide is delivered at a rate controlled by therotary valve 310 to the discharge port 312. As a result, both thehydrogen generator and the calciner are advantageously incorporated intoa single contactor vessel.

Incorporating the calciner 200 of the present invention described withreference to FIG. 2 into the calciner section 302 substantially enhancesthe performance of the hydrogen generator 300 in FIG. 3. The samedevices used to implement the several ports and the rotary valve in thehydrogen generator 300 may be used to implement the correspondingelements used in the calciner 200 of FIG. 2. Other suitable devices mayalso be used to make the ports and the rotary valve used in the calciner200 according to well-known techniques to practice various embodimentsof the present invention within the scope of the appended claims.

FIG. 4 illustrates a flow chart 400 of a method of calcining at areduced temperature according to an embodiment of the present invention.

Step 402 is the entry point of the flow chart 400.

In step 404, a solid reactant is streamed into an inlet port of acontactor vessel. The solid reactant may be, for example, calciumcarbonate produced by a hydrogen reactor.

In step 406, the solid reactant is heated to initiate the release of agas, for example, carbon dioxide, from the solid reactant. In someapplications, heating of the solid reactant may not be a necessary step.

In step 408, a purge oxidant, for example, steam, is streamed into anoxidant port of the contactor vessel to reduce the partial pressure ofthe gas released from the solid reactant to produce oxidized solidreactant. The purge oxidant also agitates the solid reactant, whichenhances the displacement of the released gas away from the oxidizedsolid reactant.

In step 410, the gas is vented from a gas port of the contactor vessel.

In step 412, the oxidized solid reactant is removed from a dischargeport of the contactor vessel. The oxidized solid reactant may then bereturned, for example, to a hydrogen reactor to repeat the separationreaction (3).

Step 414 is the exit point of the flow chart 400.

Although the method of the present invention illustrated by theflowchart description above is described and shown with reference tospecific steps performed in a specific order, these steps may becombined, sub-divided, or reordered without departing from the scope ofthe claims. Unless specifically indicated herein, the order and groupingof steps is not a limitation of the present invention.

While the invention herein disclosed has been described by means ofspecific embodiments and applications thereof, numerous modificationsand variations could be made thereto by those skilled in the art withoutdeparting from the scope of the invention set forth in the followingclaims.

1. A calcining apparatus comprising: a contactor vessel; a solidreactant inlet port coupled to the contactor vessel for streaming asolid reactant into the contactor vessel; an oxidant inlet port coupledto the contactor vessel for streaming a purge oxidant into the contactorvessel to reduce a partial pressure of a gas released from the solidreactant; a fuel inlet port coupled to the contactor vessel forintroducing fuel to heat the solid reactant; a gas vent port coupled tothe contactor vessel for venting the gas from the contactor vessel; anda solid reactant discharge port coupled to the contactor vessel forremoving the solid reactant from the contactor vessel.
 2. The calciningapparatus of claim 1 further comprising a feed stream of hydrogen gascoupled with the fuel inlet port.
 3. The calcining apparatus of claim 1further comprising a feed stream of calcium carbonate coupled with thesolid reactant inlet port.
 4. The calcining apparatus of claim 1 furthercomprising a feed stream of steam coupled with the oxidant inlet port.5. The calcining apparatus of claim 1 further comprising a hydrogen gasoutlet port for removing hydrogen gas from the contactor vessel.
 6. Thecalcining apparatus of claim 1 wherein fuel inlet port is locatedbetween the oxidant inlet port and the gas vent port.
 7. The calciningapparatus of claim 1 wherein the oxidant inlet port is located betweenthe fuel inlet port and solid reactant discharge port.
 8. The calciningapparatus of claim 1 further comprising a rotary valve adjacent to andfluidly connected with the solid reactant discharge port.
 9. A calciningapparatus comprising: a regeneration vessel including a solid reactantfeed for delivering spent solid reactant to the regeneration vessel, anoxidant gas feed for delivering oxidant gas to the vessel to reduce thepartial pressure of a gas released from the solid reactant feed, a fuelgas inlet for delivering fuel gas to the vessel, a gas vent outlet forventing a product gas from regeneration of the spent solid reactant, anda solid reactant discharge outlet for removing regenerated solidreactant from the regeneration vessel.